Manufacture of varnishes, balsams, and resins.



phases.

UNITED STATES PATENT OFFICE. ABRAHAM KRONS'IIEIN, 0F KARLSRUHE, GERMANY. MANUFACTURE OI: VARNISHES. BALSAIVIS. AND RESINS.

Specification of Letters Patent.

Patented Feb. 6, 1907.

Application filed January 26, 1900. Serial No. 2,794.

To ail whom it may concern.-

Be it known that I, ABRAHAM KRONSTEIN, doctor of philosophy, 0. subject of the Emeror of Austria, residing at Karlsruhe, Baen, in the Empire of Germany, have invented certain new and useful Improvements in the Manufacture of Varnishes, Balsams, and Resins, of which the following is a specification.

The artificial, as also the natural, thickeni of oilsi. e., the formation of varnishes, b adsams, and resins and the production of solid oils for the pur oses of manufacturing linoleumhas hereto ore been considered as mainly an oxidizing rocess, which 1s in some cases combined Wit evaporation. (M aspratt, fourth edition, Vol. 4, page 7.) The rocesses heretofore employed for the manui acture of varnishes have almost entirely been based upon application of oxidizing a ents. Theseoxidizing agents consisteither 0 solid substances giving off oxygen or of air incombination with carriers of oxygen or even of air alone.

In consequence of scientific researches made by me I have come to the conclusion that the above-mentioned assumption is not in accordance with facts. I have discovered that the thickening of oils can be carried out not only in the complete absence of air or other oxidizing agents, but also in the presence of carbonic acid, hydrogen, nitrogen, or

illuminati -gas. The roducts obtained, which are ee from oxi ation products, are distinguished from varnishes made according to customary processes by their absolute purity. In consequence hereof the im; proved recess is of considerable importance 1n avoi 'ng complicated and expensive purifications, as also in affording amuch greater yield. According to my invention the manufacture is carried out in such manner that the substances to be thickened or the mixtures of several oils are heated, preferablv, in closed vesselsthat is, practically under exclusion of air to a moderate temperature b*elow that at which decomposition commences. The thickening rocess discovered by me takes place in t ee subsequent reaction In scientific as well as in technical respects these three reaction phases will now be described in detail.

F'irst reaction phase.The thickening is to be considered as the first part'of the reaction as long as the products remain ina liquid condition at ordinary temperature or are completely liquefied after a short heating up to 250 centigrade and dissolve in one or more solvents without heating during several hours. I have found'that all the unsaturated oleaginous compounds and similar substances named hereinafter undergo this change if they contain in addition to one unsaturated group one or three or more remainingl ne ative groups, such as C,,H,,COOH or ot e'r ouble groups; but if there are only two negative remaining oups they must have an unsymmetrical disposition with res set to the unsaturated compound or group.

xperiments have been made with allyl-cinnamate, mono or diallyl malonate (B being any suitable alcohol radical) COOGH2-(JH=(JH2 euglenol, safrol, heavy cam hor-oil, styracin, (O 'nese) wood-oil, linsee -oil, camehna-oil, rape-oil, cotton-oils, maize-oil, &c. Inasmuch as the so-called vegetable dryingoils are composed of ether combinations of organic unnaturated acids with alcohol radicals, it is but natural that artificial products of the same class, such as allyl-cinnamate and allyl-malonate are capable of undergoing the same chan e if treated according to my invention as t e above-mentioned natural oils. The products of this reaction phase are varnishes, balsams, and soft resins.

Second reaction hase.In the second reaction phase, Whic takes place after a long heating, the liquid state disappears. The products are at ordinary temperature, as well as at a temperature of 250 centigradein the most cases at still higher temperature solid, soft, more or less elastic, gum-like bodies which in the beginning of the second reaction phase are also viscid. These prodnets are normally insoluble in all solvents and they obtain the property of dissolving only by melting or heatin for some time in the presence of the so vent. They behave, therefore, like the hard resins, amber, copal,

. carbonic aci &c. They are fit for the manufacture of linoleum, for the production of fine constant lac uers, &c.

ere is in particular to be pointed out the .fact that the. presence of resinssuch as cowrie-copal, colofihonymnd cork-powder does not impede t e course of the reaction.

Products of the second reaction base are obtained from allyl-cinnamate, dia yl-malonate, &c. Of the natural oils of commerce only wood-oil (termed also holzol) yields products of the second reaction phase, while the othernatural oils, heated separately, do notiproduce such products.

41rd reaction phase.-If the roduots of the second reaction phase are furt er heated, thev lose their soft, elastic, m-like state and become solid brittle bodies which behave as the natnral resins. I have found that all the products of the second reaction phase undergo the third and last change, with the exception of the roduct of wood-oil, which does not complete y lose its elasticity. The thickening process can be carried out at anfy temperature the latter only having an in uence upon the rapidit of the process. By varying the duration 0 the process and the temperature the products of the several reaction phases can be obtained. With the exception of the resin obtained from benzaldehyde by oxidation, by Hlasawitz, Barth, and Pfaunder (see Muspratt, as above) no process has heretofore been made known for obtaining bodies which entirely correspond to the natural resins in the same manner as the products of the second and third reaction phase above described.

As m improved process is carried out under exc usion of oxldizing agents the products are not oxidation products. They fr'euently surpass natura resins in regard to t eir purity. The yield is equal to the amount of raw material employed.

. Examples. I. Exam le for the manufacture of varnish.-Ten:ilograms of linseed-oil are maintained in a closed enameled vessel by means of a bath at. a constant temperature of 200 centigrade. The heating can be effected either in the presence of llluminating-gas'or or nitrogen or hydrogen.

After a heating of thirt *-six hours the separation of albumen is nished. The oil is filtered and further heated under the same conditions. After four days the product will be found after coolin to correspond completely to the varnish of commerce own as standol. The quantity produced is ten kilo ams.

I. Exam 10 E- the mnafacture of fast lacquers. en 'lograms of oil which have been freed, as descnbedin Exam 1e 1, from albumen are further heated? wit the desired quantity of copal, amber, or with the the products of the second or third reaction phase or also (2).ten kilograms of the oils which are fit to produce the above said products are heated with volatile liquids such as turpentine-oil, light camphor-oil, benzol &c.-in closed vessels to a tem erature of from 190 to 250 centigrade unt1 either the products (1) I Ive been dissolved or the oils (2) have attained the desired thickness.

II. Example ofbrilsam-Ten kilograms of allyl-malonate are heated to 170 centigr-ade twenty-four hours the oil will be thickened and will have the properties of a natural balsam. The yield is ten kilograms.

III. Emamp for the production of hard resins.Ten kilo =ams of allcyl-cinnamate are heated in a c osed enameled vessel first for thirty-six hours to 170 centigrade, after which the temperature is raised to 230? centigrade. After maintaining this temperature for thirty-six hours the process is completed. The resulting product has the a pearance of natural amber. It has about the same de- .in a closed enameled vessel. At the end of gree of hardness and can be worked in the same manner. It also behaves in thesame manner in the presence of organic and inorganic reagents. The yield is ten kilo ams. In place of the original substances t e bal s'ams produced according to Example II may also be employed for manufacturing resins.

IV. Exam le for the production of 80ft resins.Ten liilograms of eugenol are heated in a closed enameled vessel to a temperature of 180 centigrade for twenty-four hours. After cooling, the product, which will be ten kilograms, will be a solid substance which corresponds in every res ct to the natural soft resins. Like these, it is soluble in alcohol and ether.

I am aware that heating in air-tight vessels has alread been employed for resiniiying linseed-oil by eat; but this is entirely different from my invention, inasmuch as in the rocess referred to the oil was heated so as to orm a foam and to emit bubbles and increase in-volume, which is due to a decomposition of the oil and which may finally lead to solidifi cation, while when treated according to my rocess, however, no such frothing or foamng takes lace, and decomposition is carefully avoi ed, so that in the case of linseed- -oil no solidification even on prolonged heating takes place, the substances submitted to my new process being heated on] at a tem perature below the point at which decomposition sets in and which is previously ascertained in every particular case by a separate test with a small sample ofthe substance under treatment, the temperature of treatment according to my process being preferably about 80 centigrade below the temperature of decomposition.

Having thus described my invention, 1 claim as new and desire to secure by Letters Patent 1. The rocess of producing insoluble solid resin and alsam like bodies from allyl-cinnamate which consists in heating a sample of the same to ascertain the temperature of decomposition and then heating the bulk of the substance below this temperature and in the absence of oxidizing agents until solidification and insolubility is reached.

2. The process herein described of producing insoluble solid resin and balsam like bodies from allyl-cinnamate, which consists in ascertaining the temperature at which said allyl-cinnamate is decomposed, and continuously heating said allyl-cmnamate to a temperature below the temperature of decomposition and in the absence of oxidizing agents until the substance is solidified and rendered insoluble.

3. The process of roducing insoluble solid resin and balsam 11 e bodies from organic ether soluble unsaturated ester-like compounds which consists in heating a sample of the compound to ascertain the temperature of decomposition and then heating the bulk of the substance below this temperature and in the absence of oxidizing agents until solidification and insolubility is reached.

4. The process herein described of producing insoluble solid resin and balsam like bodies from organic ether soluble unsaturated ester like compounds, which consists in ascertaining the temperature of decomposition of the same, and then heating the compound below this temperature in the ab,- sence of oxidizing a ents until solidificatio and insolubilit resu t.

In witness w ereof I have hereunto si ed my name in the presence of two subscri ing witnesses.

ABRAHAM KRONSTEIN. 

